2-aminoalkanolpyridines



United States PatentO Z-AMINOALKANOLPYRI DINES Francis E. Cislak,lndianapolis, Ind., assignor to -Rjeilly Tar & Chemical Corporation,Indianapolis, 'Ind., a corporation of Indiana i No Drawing. ApplicationJuly 23, 1956, V Serial No. 599,322 I 12 Claims. (Cl. 260-296)Thisinvention relates to new chemical compounds and to the process ofmaking them; More particularly, it relates to 2-aminoalkanolpyridineshaving the general formula:

where x and ,y are 0, 1, or 2 and they may be alike or different, A andA are either hydrogen or hydroxyl, R is hydrogen or lower alkyl, and Rishydrogen, lower alkyl,

hydroxy-lower alkyl, benzyl or benzhydryl.

In general the compounds of my invention maybe pre pared by reacting analkanolpyridine with sodarm'de. The equation below portrays thepreparation of 2l-amino-4 -(lpropan-S -01) pyridine:

NaNH:

EXAMPLE 1 2-amin0-4-(1 -prpa n3-0l) pyridine CHgCHzOHtOH About 90 gramsof finely divided sodamide is dispersed in about 500 cc. of anhydrousxylene. The mixture of sodamide and xylene is heated to about 100-420 C.During the heating up and during the subsequent reaction period thesodamide-xylene mixture is continually'stirred. To the hot dispersion ofsodamide in xylene there is added in small portions, 137 grams of4-(-1:propan-S-oHpYfl-dine. Hydrogen is evolved by theaminationyreactiont'i At first the'rate of hydrogen evolution is quiterapid. When the hydrogen evolution begins slowing down, the temperatureof the reaction mixture is raised to about l30=-14,0 C. and ismaintained at this temperature for about threeto four hours after all ofthe propanolpyrldine has been added. When the reaction is completed,about 200 cc. of the xylene is removed by vacuum distillation. To theresidue there is added first about 50 cc. of methanol, and

then about 100 cc. of water. The 2-amino-4(1-p'ropan- 3-ol)pyridineformed is isolated in any suitablemanner. One way of isolating the2-a-mino-4-(l-propanrS-Ohpyridine is as follows: .To the mixture abovethere is added 20Q-300 cc. of fl-picoline and the mixture isthoroughly2,807,619 Patenteds t. 24, 1 957 v2 agitated. Upon settling, two layersare formed, an-aqueous caustic soda layer and the 4-picoline layercontaining the 2-arnino-4-( l-propan-3-0l)pyridine. The 4-picoline layeris separated. Some of theaqueous caustic layer is dissolved in the4-picoline layer; this is neutralized by treatment with carbon dioxide.The 2-amino-4-(1- propan-3-ol)pyridine is separated by fractionaldistillation under vacuum. j 1

In place of the sodamide I may use other alkali amides, such, forexample, as potassium amide.

In place of xylene as the reaction medium, I may use various otherhydrocarbons, such as toluene, cumene,rand the like, or I may usedimeth-ylaniline.

In general it is desirable to carry out the reactionrat the lowestpossible temperature. I find that a temperature EXAMPLE 2 2-amin0-6-(11-pr0'pan-3-0l) pyridine K .The procedure of Example l is repeated withthe exception that 2(l-propan-3-ol) pyridine is used instead of the4-(l-,propan-3-ol)pyridine. f

EXAMPLE 3 e 3- 2 -z zmin0pyridyl carbinvl CHaOH N The procedure ofExample 1 is repeated with the exception that fi-pyridylcarbinol is usedin place of the 4- 1-propan-3-ol) pyridine. I believe that in additionto the 2-amino-3-methanolpyridine, some 2-amino-5-methanolpyridine isformed.

EXAMPLE 4 2-amino-3-ethyl-6- (1 -ethan'-2-0l)pyridine HO CHzCHr- N NH;

The procedure of Example 1 is repeated with the exception that I l-ethyl-6-(l-ethan-2-ol)pyridine is used in place of the4-(l-propan-3-ol)pyridine.

EXAMPLE 5 2-amino-6-(I-ethan-Z-oDpyridine HOCHzCHr N 2 The procedure ofExample 1 is repeated with the exccption that 2-(1ethan-2-ol)-4-(l-propan-3-ol)pyridine is used in place of the 4-(l-propan-3-ol)pyridine and 110 .grams of sodamide are used in place of the 90 gramsused in Example 1.

EXAMPLE 7 Zamino-4-(3-pentan-1 :S-diol) pyridine The procedure ofExample 1 is repeated with the exception that4-(3-pentan-l:5-diol)pyridine is used in place of the4-(l-propan-3-ol)pyridine and 110 grams of sodamide are used in place ofthe 90 grams used in .Example 1.

EXAMPLE 8 6-(2-amin0pyridyl) carbinol My2-amino-6-(l-ethan-2-ol)pyridine may be used to make 2-amino-6-vinylpyridine.

noomomarn:

NaOH

The 2-aminoalkanolpyridines of my invention are amino-alcohols. Theyhave chemical properties associated with amino-alcohols and are capableof entering into the same type of reactions as other amino-alcohols,within the limitations imposed by the pyridine nucleus. The2-aminoalkanolpyridine soaps, such as the stearate, may be used asemulsion stabilizers.

Some of my 2-aminoalkanolypyridines, such, for example, as the2-amino-4-(3-pentan-1:S-diol) pyridine are useful in the formulation ofpolyurethane type resins. The presence of the two hydroxyl groups aswell as the amino group makes this compound useful both as a componentof the polyester as well as an internal catalyst.

used is 6-(1-ethan-2-ol)pyridine.

Some of the 2-aminopyridylcarbinols claimed in this application may alsobe made by the process described and claimed in my co-pendingapplication Serial No. 599,323 filed even date herewith.

In said co-pending application I describe and claim the preparation of4-(2-aminopyridyl) carbinols and 6-(2- aminopyridyl) carbinols by aprocess comprising refluxing with acetic anhydride a2-acetamido-4-alkylpyridine- N-oxide or aZ-acetamido-6-alkylpyridine-Noxide. Also claimed in said co-pendingapplication are phenyl and diphenyl 4-(2aminopyridyl) carbinols and6-(2-aminopyridyl) carbinols.

I claim as my invention:

1. A compound of the class consisting of Z-aminoalkanolpyridines havingthe following general formulae:

and

'where x is an integer selected from the group consisting of 0, l, and2, R is one of the group consisting of hydrogen and lower alkyl, and Ris one of the group consisting of lower alkyl, hydrogen, hydroxyloweralkyl, and benzyl.

N OH

where x is an integer selected from the group consisting of 0, 1, and 2,R is one of the group consisting of hydrogen and lower alkyl, and R isone of the group consisting of lower alkyl, hydrogen, hydroxy-alkyl, andbenzyl.

8. The process of claim 7 wherein the alkanolpyridine used is4-(l-propan-3-ol) pyridine.

9. The process of claim 7 wherein the alkanolpyridine and used is6-(1-propan-3-ol)pyridine.

10. The process of claim 7 wherein the alkanolpyridine used is3-ethyl-6- l-ethan-Z-ol) pyridine.

11. The process of claim 7 wherein the alkanolpyridine used is3-ethyl-6-( l-propan-3-ol)pyridine.

12. The process of claim 7. wherein the alkanolpyridine References Citedin the file of this patent FOREIGN PATENTS OTHER REFERENCES Berezovskii:Chem. Abstracts, vol. 46, col. 3282 (1952).

1. A COMPOUND OF THE CLASS CONSISTING OF 2-AMINOALKANOLPYRIDINES HAVINGTHE FOLLOWING GENERAL FORMULAE: